Hard surface cleaning compositions

ABSTRACT

The present invention is directed to a sprayable, acidic hard surface cleaning and/or disinfecting composition which contains suspended inclusions which appear as visibly discernible, discrete particulate materials, preferably where said discrete particulate materials are based on alginates. The composition contains a thiclcener which comprises both gellan gum and Xanthan gum.

The present invention relates to sprayable disinfecting hard surfacecleaning compositions. More particularly the present invention relatestothickened lavatory cleaning compositions which provide a cleaning anddisinfecting effect to hard surfaces, and which include visiblydiscernible inclusions.

Cleaning compositions which also provide a disinfecting or sanitizingeffect are commercially important products. Such compositions enjoy awide field of utility in assisting in the removal of stains and grimefrom surfaces, especially those characterized as useful with “hardsurfaces”. Hard surfaces are those which are frequently encountered inlavatories such as lavatory fixtures such as toilets, shower stalls,bathtubs, bidets, sinks, etc., as well as countertops, walls, floors,etc. Two types of commonly encountered stains in lavatories include“hard water” stains and “soap scum” stains. Such hard surfaces, and suchstains, may also be found in different environments as well, includingkitchens, hospitals, etc.

Various formulations in compositions of cleaning agents have beenproduced and are known to the art which cleaning agents are generallysuited for one type of stain but not necessarily for both classes ofstains. For example, it is known to the art that highly acidic cleaningagents comprising strong acids, such as hydrochloric acids, are usefulin the removal of hard water stains. However, the presence of strongacids is known to be an irritant to the skin and further offers thepotential of toxicological danger. Other classes of cleaningcompositions and formulations are known to be useful upon soap scumstains, however, generally such compositions comprise an organic and/orinorganic acid, one or more synthetic detergents from commonlyrecognized classes such as those described in U.S. Pat. No. 5,061,393;U.S. Pat. No. 5,008,030; U.S. Pat. No. 4,759,867; U.S. Pat. No.5,192,460; U.S. Pat. No. 5,039,441. Generally, the compositionsdescribed in these patents are claimed to be effective in the removal ofsoap scum stains from such hard surfaces and may find further limiteduse in other classes of stains.

However, the formulations of most of the compositions within theaforementioned patents generally have relatively high amounts of acids(organic and/or inorganic) which raises toxicological concerns, andfurther none of the above patents provide any disinfecting properties.

While many disinfecting hard surface cleaning compositions are known tothe art, there is nonetheless a need for further improved compositionsin the art.

According to the one aspect of the invention, there is provided asprayable hard surface cleaning and/or disinfecting composition whichcomprises (preferably consists essentially of):

a thickener constituent which comprises both gellan gum and xanthan gum;

at least one nonionic surfactant;

an acid constituent;

suspended inclusions which appear as visibly discernible, discreteparticulate materials, preferably where said discrete particulatematerials are based on alginates;

optionally, at least one further detersive surfactant selected fromamphoteric and zwitterionic surfactants;

optinally at least one anionic surfactant;

optionally, at least one organic solvent;

optionally, one or more constituents for improving the aesthetic orfunctional features of the inventive compositions; and;

water.

In further aspects of the invention there are provided processes for theproduction of the aforesaid compositions.

It is yet a further object of the invention to provide a readilysprayable cleaning composition which features the benefits describedabove.

It is a further object of the invention to provide a process for theimprovement of the simultaneous cleaning and sanitization of hardsurfaces, which process comprises the step of: providing a compositionas outlined above, and applying an effective amount to a hard surfacerequiring such treatment.

Particularly preferred compositions according to the invention areacidic in character, are effective in the removal of both soap scumstains and hard water stains, and which compositions provide aneffective sanitizing effect to hard surfaces. Further, particularlypreferred sprayable compositions may be dispensed from a manuallyoperable trigger pump spray apparatus and the composition provided bysuch device has visibly discernible, visibly discrete particulatematerials on a treated hard surface.

The inventive compositions necessarily comprise a thickener constituent.In addition to the gellan gum and the xanthan gum, one or more furtherthickeners may also be included in the inventive compositions. By way ofnon-limiting example such further thickeners include one or more ofcellulose, alkyl celluloses, alkoxy celluloses, hydroxy alkylcelluloses, alkyl hydroxy alkyl celluloses, carboxy alkyl celluloses,carboxy alkyl hydroxy alkyl celluloses, and mixtures thereof. Examplesof the cellulose derivatives include ethyl cellulose, hydroxy ethylcellulose, hydroxy propyl cellulose, carboxy methyl cellulose, carboxymethyl hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxy propylmethyl cellulose, and ethyl hydroxy ethyl cellulose. Preferably, thethickener constituent is a mixture of xanthan gum and gellan gum to theexclusion of other thickener constituents described herein. Furtherexamples of preferred thickener constituents are described in theExamples.

The gellan gum and the xanthan gum may be present in the thickenerconstituent in any relative amounts with respect to each other.Desirably however the ratio of gellan gum to xanthan gum on a respectiveparts by weight basis is from 1:1-10, preferably 1:1-5 but morepreferably from 1:1 to 1:2 parts by weight. These preferred respectiveweight ratios may be used in the presence of further thickeners formingthe thickener constituent, and especially preferably are used in theabsence of further thickeners. The present inventors have observed thatthe combination of gellan gum and xanthan gum, especially in therespective weight ratios described above are particularly effective inproviding the desirable rheological properties to the sprayablecompositions. Even minor amounts of gellan gum when combined withxanthan gum may provide surprisingly good thickening and desirablerheological properties.

The amount of thickener present in the composition may be any amountwhich is effective in suspending the suspended inclusions as hereinafterdescribed. Desirably the composition of the present of invention isthickened to a viscosity range of from about 25 to about 300 centipoise,preferably to a viscosity of from about 100 to about 300 centipoise,more preferably is in the range of about 50-200 centipoise measured atroom temperature, on a LVTDV IIBrookfield viscometer, spindle #1, at 30rpm, measured at 25° C. Generally good thickening has been observed whenthe total amount of the thickeners are present in amount from about0.001 to about 5% by weight, more preferably from about 0.001 to about3% by weight, more preferably from about 0.001-1.5% wt, still morepreferably from about 0.01-0.50% wt. and most preferably the totalamount of the thickeners are present in the inventive compositions inamount of from about 0.03% wt. to about 0.20% wt.

Preferably other thickening materials known to the art, particularlythose based on synthetic polymers such as acrylic acid copolymers, e.g.Carbopol® materials, as well as those based on clays are absent from theinventive compositions.

The inventive compositions further requires at least one nonionicsurfactant. Generally any nonionic surfactant material may be used inthe inventive compositions. Practically any hydrophobic compound havinga carboxy, hydroxy, amido, or amino group with a free hydrogen attachedto the nitrogen can be condensed with an alkylene oxide, especiallyethylene oxide or with the polyhydration product thereof, a polyalkyleneglycol, especially polyethylene glycol, to form a water soluble or waterdispersible nonionic surfactant compound. By way of non-limitingexample, particularly examples of suitable nonionic surfactants whichmay be used in the present invention include the following:

One class of useful nonionic surfactants include polyalkylene oxidecondensates of alkyl phenols. These compounds include the condensationproducts of alkyl phenols having an alkyl group containing from about 6to 12 carbon atoms in either a straight chain or branched chainconfiguration with an alkylene oxide, especially an ethylene oxide, theethylene oxide being present in an amount equal to 5 to 25 moles ofethylene oxide per mole of alkyl phenol. The alkyl substituent in suchcompounds can be derived, for example, from polymerized propylene,diisobutylene and the like. Examples of compounds of this type includenonyl phenol condensed with about 9.5 moles of ethylene oxide per moleof nonyl phenol; dodecylphenol condensed with about 12 moles of ethyleneoxide per mole of phenol; dinonyl phenol condensed with about 15 molesof ethylene oxide per mole of phenol and diisooctyl phenol condensedwith about 15 moles of ethylene oxide per mole of phenol.

A further class of useful nonionic surfactants include the condensationproducts of aliphatic alcohols with from about 1 to about 60 moles of analkylene oxide, especially an ethylene oxide. The alkyl chain of thealiphatic alcohol can either be straight or branched, primary orsecondary, and generally contains from about 8 to about 22 carbon atoms.Examples of such ethoxylated alcohols include the condensation productof myristyl alcohol condensed with about 10 moles of ethylene oxide permole of alcohol and the condensation product of about 9 moles ofethylene oxide with coconut alcohol (a mixture of fatty alcohols withalkyl chains varying in length from about 10 to 14 carbon atoms). Otherexamples are those C6-C11 straight-chain alcohols which are ethoxylatedwith from about 3 to about 6 moles of ethylene oxide. Their derivationis well known in the art. Examples include Alfonic® 810-4.5, which isdescribed in product literature from Sasol as a C8-10 having an averagemolecular weight of 356, an ethylene oxide content of about 4.85 moles(about 60 wt. %), and an HLB of about 12; Alfonic® 810-2, which isdescribed in product literature as a C8-C10 having an average molecularweight of 242, an ethylene oxide content of about 2.1 moles (about 40wt. %), and an HLB of about 12; and Alfonic® 610-3.5, which is describedin product literature as having an average molecular weight of 276, anethylene oxide content of about 3.1 moles (about 50 wt. %), and an HLBof 10. Other examples of alcohol ethoxylates are C10 oxo-alcoholethoxylates available from BASF under the Lutensol® ON tradename. Theyare available in grades containing from about 3 to about 11 moles ofethylene oxide (available under the names Lutensol® ON 30; Lutensol® ON50; Lutensol® ON 60; Lutensol® ON 65; Lutensol® ON 66; Lutensol® ON 70;Lutensol® ON 80; and Lutensol®ON 110). Other examples of ethoxylatedalcohols include the Neodol® 91 series non-ionic surfactants availablefrom Shell Chemical Company which are described as C9-C11 ethoxylatedalcohols. The Neodol® 91 series non-ionic surfactants of interestinclude Neodol® 91-2.5, Neodol® 91-6, and Neodol® 91-8. Neodol® 91-2.5has been described as having about 2.5 ethoxy groups per molecule;Neodol 91-6 has been described as having about 6 ethoxy groups permolecule; and Neodol 91-8 has been described as having about 8 ethoxygroups per molecule.Further examples of ethoxylated alcohols include theRhodasurf® DA series non-ionic surfactants available from Rhodia whichare described to be branched isodecyl alcohol ethoxylates. Rhodasurf®DA-530 has been described as having 4 moles of ethoxylation and an HLBof 10.5; Rhodasurf® DA-630 has been described as having 6 moles ofethoxylation with an HLB of 12.5; and Rhodasurf® DA-639 is a 90%solution of DA-630. Further examples of ethoxylated alcohols includethose from Tomah Products (Milton, Wis.) under the Tomadol® tradenamewith the formula RO(CH2CH2O)nH where R is the primary linear alcohol andn is the total number of moles of ethylene oxide. The ethoxylatedalcohol series from Tomah include 91-2.5; 91-6; 91-8—where R is linearC9/C10/C11 and n is 2.5, 6, or 8; 1-3; 1-5; 1-7; 1-73B; 1-9; where R islinear C11 and n is 3, 5, 7 or 9; 23-1; 23-3; 23-5; 23-6.5—where R islinear C12/C13 and n is 1, 3, 5, or 6.5; 25-3; 25-7; 25-9; 25-12—whereis linear C12/C13/C14/C15 and n is 3, 7, 9, or 12; and 45-7; 45-13—whereR is linear C14/C15 and n is 7 or 13.

A further class of useful nonionic surfactants include primary andsecondary linear and branched alcohol ethoxylates, such as those basedon C6-C18 alcohols which further include an average of from 2 to 80moles of ethoxylation per mol of alcohol. These examples include theGenapol® UD (ex. Clariant, Muttenz, Switzerland) described under thetradenames Genapol® UD 030, C11-oxo-alcohol polyglycol ether with 3 EO;Genapol® UD, 050 C11-oxo-alcohol polyglycol ether with 5 EO; Genapol® UD070, C11-oxo-alcohol polyglycol ether with 7 EO; Genapol® UD 080,C11-oxo-alcohol polyglycol ether with 8 EO; Genapol® UD 088,C11-oxo-alcohol polyglycol ether with 8 EO; and Genapol® UD 110,C11-oxo-alcohol polyglycol ether with 11 EO.

A further class of useful nonionic surfactants include those surfactantshaving a formula RO(CH2CH20)nH wherein R is a mixture of linear, evencarbon-number hydrocarbon chains ranging from C12H25 to C16H33 and nrepresents the number of repeating units and is a number of from about 1to about 12. Surfactants of this formula are presently marketed underthe Genapol® tradename(ex. Clariant), which surfactants include the“26-L” series of the general formula RO(CH2CH20)nH wherein R is amixture of linear, even carbon-number hydrocarbon chains ranging fromC12H25 to C16H33 and n represents the number of repeating units and is anumber of from 1 to about 12, such as 26-L-1, 26-L-1.6, 26-L-2, 26-L-3,26-L-5, 26-L-45, 26-L-50, 26-L-60, 26-L-60N, 26-L-75, 26-L-80, 26-L-98N,and the 24-L series, derived from synthetic sources and typicallycontain about 55% C12 and 45% C14 alcohols, such as 24-L-3, 24-L-45,24-L-50, 24-L-60, 24-L-60N, 24-L-75, 24-L-92, and 24L-98N, all soldunder the Genapol® tradename.

A further class of useful nonionic surfactants include alkoxy blockcopolymers, and in particular, compounds based on ethoxy/propoxy blockcopolymers. Polymeric alkylene oxide block copolymers include nonionicsurfactants in which the major portion of the molecule is made up ofblock polymeric C2-C4 alkylene oxides. Such nonionic surfactants, whilepreferably built up from an alkylene oxide chain starting group, and canhave as a starting nucleus almost any active hydrogen containing groupincluding, without limitation, amides, phenols, thiols and secondaryalcohols.

One group of such useful nonionic surfactants containing thecharacteristic alkylene oxide blocks are those which may be generallyrepresented by the formula (A):HO-(EO)_(x)(PO)_(y)(EO)_(z)—H   (A)where EO represents ethylene oxide,

-   -   PO represents propylene oxide,    -   y equals at least 15,

(EO)x+y equals 20 to 50% of the total weight of said compounds, and, thetotal molecular weight is preferably in the range of about 2000 to15,000. These surfactants are available under the PLURONIC® (ex. BASF)or EMULGEN® (ex. Kao.)

A further group of such useful nonionic surfactants containing thecharacteristic alkylene oxide blocks are those can be represented by theformula (B):R-(EO,PO)_(a)(EO,PO)_(b)—H   (B)wherein R is an alkyl, aryl or aralkyl group, where the R group contains1 to 20 carbon atoms, the weight percent of EO is within the range of 0to 45% in one of the blocks a, b, and within the range of 60 to 100% inthe other of the blocks a, b, and the total number of moles of combinedEO and PO is in the range of 6 to 125 moles, with 1 to 50 moles in thePO rich block and 5 to 100 moles in the EO rich block. Specific nonionicsurfactants which in general are encompassed by Formula B include butoxyderivatives of propylene oxide/ethylene oxide block polymers havingmolecular weights within the range of about 2000-5000.

Still further examples of useful nonionic surfactants include thosewhich can be represented by formula (C) as follows:RO—(BO)_(n)(EO)_(x)—H   (C)wherein EO represents ethylene oxide,

-   -   BO represents butylene oxide,        R is an alkyl group containing I to 20 carbon atoms,    -   n is about 5-15 and x is about 5-15.        Yet further useful nonionic surfactants include those which may        be represented by the following formula (D):        HO—(EO)_(x)(BO)_(n)(EO)_(y)—H   (D)        wherein EO represents ethylene oxide,    -   BO represents butylene oxide,        n is about 5-15, preferably about 15,    -   x is about 5-15, preferably about 15, and    -   y is about 5-15, preferably about 15.        Still further exemplary useful nonionic block copolymer        surfactants include ethoxylated derivatives of propoxylated        ethylene diamine, which may be represented by the following        formula:        where (EO) represents ethoxy,    -   (PO) represents propoxy,        the amount of (PO)x is such as to provide a molecular weight        prior to ethoxylation of about 300 to 7500, and the amount        of(EO)y is such as to provide about 20% to 90% of the total        weight of said compound.

Particularly preferred nonionic block copolymers include those based ona polymeric ethoxy/propoxy units which may also be used include thosepresently commercially available in the PLURAFAC® series of blockcopolymers (ex. BASF) These are described to be nonionic surfactantsbased on ethoxy/propoxy block copolymers, conveniently available in aliquid form from its supplier. One particularly preferred nonionic blockcopolymer is PLURAFAC® SL-62 which is described to be a nonionicsurfactant based on ethoxy/propoxy block copolymers having an average offrom about 1-3 moles propoxy groups, and 412 moles ethoxy groups andhaving a total molecular weight from about 600-650. In certain preferredembodiments of the inventive composition present the sole nonionicsurfactant present is a nonionic surfactant based on ethoxy/propoxyunits, and especially is a nonionic block copolymer as described withreference to PLURAFAC® SL-62.

Further useful non-ionic surfactants which may be used in the inventivecompositions include those presently marketed under the trade namePluronics® (ex. BASF). The compounds are formed by condensing ethyleneoxide with a hydrophobic base formed by the condensation of propyleneoxide with propylene glycol. The molecular weight of the hydrophobicportion of the molecule is of the order of 950 to 4,000 and preferably200 to 2,500. The addition of polyoxyethylene radicals of thehydrophobic portion tends to increase the solubility of the molecule asa whole so as to make the surfactant water-soluble. The molecular weightof the block polymers varies from 1,000 to 15,000 and the polyethyleneoxide content may comprise 20% to 80% by weight. Preferably, thesesurfactants are in liquid form and particularly satisfactory surfactantsare available as those marketed as Pluronics® L62 and Pluronics® L64.Alkylmonoglyocosides and alkylpolyglycosides which find use in thepresent inventive compositions include known nonionic surfactants whichare alkaline and electrolyte stable. Alkylmonoglycosides andalkylpolyglycosides are prepared generally by reacting a monosaccharide,or a compound hydrolyzable to a monosaccharide with an alcohol such as afatty alcohol in an acid medium. Various glycoside and polyglycosidecompounds including alkoxylated glycosides and processes for making themare disclosed in U.S. Pat. Nos. 2,974,134; 3,219,656; 3,598,865;3,640,998; 3,707,535, 3,772,269; 3,839,318; 3,974,138; 4,223,129 and4,528,106 the contents of which are incorporated by reference.

One exemplary group of such useful alkylpolyglycosides include thoseaccording to the formula:RO—(C_(n)H_(2n)O)_(r)-(Z)_(x)wherein:

-   R is a hydrophobic group selected from alkyl groups, alkylphenyl    groups, hydroxyalkylphenyl groups as well as mixtures thereof,    wherein the alkyl groups may be straight chained or branched, and    which contain from about 8 to about 18 carbon atoms,-   n has a value of 2-8, especially a value of 2 or 3;-   r is an integer from 0 to 10, but is preferably 0,-   Z is derived from glucose; and,-   x is a value from about 1 to 8, preferably from about 1.5 to 5.

Preferably the alkylpolyglycosides are nonionic fattyalkylpolyglucosides which contain a straight chain or branched chainC8-C15 alkyl group, and have an average of from about 1 to 5 glucoseunits per fatty alkylpolyglucoside molecule. More preferably, thenonionic fatty alkylpolyglucosides which contain straight chain orbranched C8-C15 alkyl group, and have an average of from about 1 toabout 2 glucose units per fatty alkylpolyglucoside molecule.

A further exemplary group of alkyl glycoside surfactants suitable foruse in the practice of this invention may be presented by the followingformula (A):RO—(R¹O)y-(G)xZb   (A)wherein:

-   R is a monovalent organic radical containing from about 6 to about    30, preferably from about 8 to 18 carbon atoms,-   R¹ is a divalent hydrocarbon radical containing from about 2 to    about 4 carbon atoms,-   y is a number which has an average value from about 0 to about 1 and    is preferably 0,-   G is a moiety derived from a reducing saccharide containing 5 or 6    carbon atoms; and,-   x is a number having an average value from about 1 to 5 (preferably    from 1.1 to 2);-   Z is O₂M¹,    O(CH₂), CO₂M¹, OSO₃M¹, or O(CH₂)SO₃M¹; R₂ is (CH₂)CO₂M¹ or    CH═CHCO₂M¹; (with the proviso that Z can be O₂M¹ only if Z is in    place of a primary hydroxyl group in which the primary    hydroxyl-bearing carbon atom,—CH₂OH, is oxidized to form a    group)-   b is a number of from 0 to 3x+1 preferably an average of from 0.5 to    2 per glycosal group; p is 1 to 10, M¹ is H⁺ or an organic or    inorganic counterion, particularly cations such as, for example, an    alkali metal cation, ammonium cation, monoethanolamine cation or    calcium cation. As defined in Formula (A) above, R is generally the    residue of a fatty alcohol having from about 8 to 30 and preferably    8 to 18 carbon atoms. Examples of such alkylglycosides as described    above include, for example APG 325 CS Glycoside® which is described    as being a 50% C₉-C₁₁ alkyl polyglycoside, also commonly referred to    as D-glucopyranoside, (commercially available from Henkel KGBA) and    Glucopon® 625 CS which is described as being a 50% C₁₀-C₁₆ alkyl    polyglycoside, also commonly referred to as a D-glucopyranoside,    (ex. Henkel).

Further nonionic surfactants which may be included in the inventivecompositions include alkoxylated alkanolamides, preferably C₈-C₂₄ alkyldi(C2-C3 alkanol amides), as represented by the following formula:R⁵—CO—NH—R⁶—OHwherein R⁵ is a branched or straight chain C₈-C₂₄ alkyl radical,preferably a C₁₀-C₁₆ alkyl radical and more preferably a C₁₂-C₁₄ alkylradical, and R⁶ is a C₁-C₄ alkyl radical, preferably an ethyl radical.

The inventive compositions may also include a nonionic amine oxideconstituent. Exemplary amine oxides include:

(A) Alkyl di(lower alkyl) amine oxides in which the alkyl group hasabout 10-20, and preferably 12-16 carbon atoms, and can be straight orbranched chain, saturated or unsaturated. The lower alkyl groups includebetween 1 and 7 carbon atoms. Examples include lauryl dimethyl amineoxide, myristyl dimethyl amine oxide, and those in which the alkyl groupis a mixture of different amine oxide, dimethyl cocoamine oxide,dimethyl (hydrogenated tallow) amine oxide, and myristyl/palmityldimethyl amine oxide;

(B) Alkyl di(hydroxy lower alkyl) amine oxides in which the alkyl grouphas about 10-20, and preferably 12-16 carbon atoms, and can be straightor branched chain, saturated or unsaturated. Examples arebis(2-hydroxyethyl) cocoamine oxide, bis(2-hydroxyethyl)tallowamineoxide; and bis(2-hydroxyethyl)stearylamine oxide;

(C) Alkylamidopropyl di(lower alkyl) amine oxides in which the alkylgroup has about 10-20, and preferably 12-16 carbon atoms, and can bestraight or branched chain, saturated or unsaturated. Examples arecocoamidopropyl diraethyl amine oxide and tallowamidopropyl dimethylamine oxide; and

(D) Alkylmorpholine oxides in which the alkyl group has about 10-20, andpreferably 12-16 carbon atoms, and can be straight or branched chain,saturated or unsaturated.

Preferably the amine oxide constituent is an alkyl di(lower alkyl) amineoxide as denoted above and which may be represented by the followingstructure:

wherein each:

R₁ is a straight chained C₁-C₄ alkyl group, preferably both R₁ aremethyl groups; and,

R₂ is a straight chained C₈-C₁₈ alkyl group, preferably is C₁₀-C₁₄ alkylgroup, most preferably is a C₁₂ alkyl group. Each of the alkyl groupsmay be linear or branched, but most preferably are linear. Mostpreferably the amine oxide constituent is lauryl dimethyl amine oxide.Technical grade mixtures of two or more amine oxides may be used,wherein amine oxides of varying chains of the R₂ group are present.Preferably, the amine oxides used in the present invention include R₂groups which comprise at least 50% wt., preferably at least 60% wt. ofC₁₂ alkyl groups and at least 25% wt. of C₁₄ alkyl groups, with not morethan 15% wt. of C₁₆, C₁₈ or higher aikyl groups as the R₂ group.

Of course the nonionic surfactant constituent, when present, my comprisetwo or more nonionic surfactants. The nonionic surfactant is present inthe compositions of the present invention in an amount of from about 0.1to about 10% by weight, more preferably is present in an amount of fromabout 0.1-5% wt., yet more preferably in an amount of from about 0.25-2%wt., and most preferably in an amount of from about 0.3-1.5% wt.

The present inventive compositions necessarily comprise an acidconstituent which be a water soluble inorganic acid, or a water solubleorganic acids. By way of non-limiting example useful inorganic acidsinclude hydrochloric acid, phosphonic, and sulfuric acid. With respectto water soluble organic acids, generally include at least one carbonatom, and include at least one carboxyl group (—COOH) in its structure.Preferred are water soluble organic acids which contain from 1 to about6 carbon atoms, and at least one carboxyl group as noted. Particularlypreferred amongst such organic acids are: formic acid, citric acid,sorbic acid, acetic acid, boric acid, maleic acid, adipic acid, lacticacid, malic acid, malonic acid, glycolic acid, and mixtures thereof.According to certain preferred embodiments however, the acid constituentis a combination of citric acid in combination with at least one furtheracid selected from the group consisting of sorbic acid, acetic acid,boric acid, formic acid, maleic acid, adipic acid, lactic acid, malicacid, malonic acid, and glycolic acid. Most preferably, the acidconstituent is a combination of citric acid with lactic acid, glycolicacid or malic acid.

As the inventive compositions are necessarily acidic in nature (pH <7.0)there should be sufficient acid present in the composition such that thepH of the composition is desirably less than 6, preferably from about 2to about 3.5, more preferably from about 2.8 to about 3.3, and mostpreferably from about 3.0 to about 3.3. Of course mixtures of two ormore acids may be used, and the acid constituent may be present in anyeffective amount. Desirably however, the acid constituents is present inan amount not in excess of 10% wt. based on the total weight of thecompositions; preferably the acid constituent is present in an amount offrom about 0.05-8% wt., more preferably from about 1-6% wt., and mostpreferably is present in an amount of from about 2% wt. to about 5% wt.The acid constituent of the inventive formulations provide free aciditywithin the cleaning composition, which free acid reacts with the fattyacid metal salts which are comprised within soap scum stains releasingthe metal ions and freeing the fatty acid, which facilitates the removalof these undesired stains from hard surfaces. These acids also sequesterthe resulting free metal ions which are released from the soap scumstains. Also where the acids are selected to feature disinfectingproperties, they concomitantly provide anti-microbial activity necessaryto disinfect the cleaned surface.

As a necessary constituent, the inventive compositions include suspendedinclusions based on alginates. These suspended inclusions appear asvisibly discernible, discrete particulate materials to the consumer ofthe inventive compositions. These suspended inclusions desirably appearas small discrete visible particles suspended within the composition,particularly by a consumer having normal “20/20” vision. It is to beunderstood however that not all of the particulate materials present inthe inventive composition need be visibly discernible as a portion ofthe particulate materials may be smaller than the visible threshold ofthe consumer having normal vision. It is nonetheless required that atleast a portion of the particulate materials present in the inventivecomposition need be visibly discernible as discrete particles.

Desirably the alginate based particulate materials are supplied to havean average particle size in the range of about 50 μm to about 1000 μm,preferably in the range of about 350 μm to about 700 μm, most preferablyin the range of about 550 μm to about 650 μm, and especially preferablyin the range of about 575 μm to about 625 μm. Desirably the averageparticle size of these particulate materials represents that at least85% of the particles, more preferably at least 90%, still morepreferably at least 92%, and most preferably at least 95% of theparticles present are within a specified range. The suspended inclusionspresent in the inventive compositions are based on alginates althoughother visibly discernible, discrete particulate materials may be used aswell, or in the place of alginate based materials. However the preferredsuspended inclusions are based on alginates.

Alginate based particulate materials used for the suspended inclusionsin the inventive compositions may be formed from an alginate or salts ofalginic acid such as potassium alginate, calcium alginate or sodiumalginate salts, and advantageously may be conveniently harvested fromnaturally occurring seaweed especially of the species Laminaria whereinthe sodium alginate form predominates. Alginates typically consist ofsequences of α-L-guluronic acid and β-D-mannuronic acid which may bepresent in the alginate in various differing ratios. The term “beads”conveniently describes the geometry of the alginate based particulatematerials as when these are formed form an aqueous slurry containing analginate such as sodium alginate with one or more further constituentsand then expelled to form individual particles or droplets, thecoalescing aqueous slurry may form generally spherical particles, hencethe term “beads”. Of course, other processes for the formation ofalginate based suspended inclusions are also contemplated as beinguseful in conjunction with the present invention such as processeswherein the alginate optionally containing one or more furtherconstituents is comminuted by other methods, such as milling, grindingor other known art technique. In such instances the comminuted alginatebased suspended inclusions may not necessarily form generally sphericalparticles but may form individual particles of irregular geometry. Insuch an instance the largest dimension of such individual particles ofirregular geometry are used as the basis for determining the averageparticle size of the

The alginate based particulate materials may contain from about 0.5% wt.to 100% wt. of an alginate or alginate salt, although quite frequentlythe amount of alginate in the alginate based particulate materials aremuch less, generally on from about 0.5% wt. to about 10% wt., morepreferably from about 0.5% wt. to about 5% wt. Such alginate basedparticulate materials may be conveniently referred to as “alginatebeads”. Such alginate beads may be formed by a variety of known artprocesses including those described in the background section ofPCT/US95/08313 to Thomas et al., as well as in U.S. Pat. No. 6,467,699B1, the contents of which are incorporated by reference. Alternatelysuch alginate based particulate materials may be commercially purchasedfrom various suppliers, including geniaLab BioTechnologie (Braunschwig,Germany). As noted the composition of the alginate based particulatematerials may include only a small proportion of an alginate or alginatesalt, and may include one or more further non-alginate materialsespecially one or more inorganic materials such as titanium dioxidewhich improves the opacity, hence the visibility of the beads, as wellas one or more coloring agents such as pigments such as ultramarineblue, said coloring agents which also improve the aesthetic appearanceof the beads. Other further non-alginate materials not recited hereinmay also be include in the composition of the alginate based particulatematerials. The alginate based particulate materials may be composed of amajor proportion of water which is entrained within the structure of thediscrete alginate based particulates and due to the highly porouscharacter of alginates when in an aqueous compositions 80% wt., andusually 90% wt. or even greater of the mass of the discrete alginatebased particulates may be water with the remaining balance to 100% wt.being the alginate or alginate salt, and one or more furthernon-alginate materials. Conveniently such alginate based particulatematerials may be prepared, stored and sold as a slurry of discretealginate based particulates in an aqueous-based carrier compositionwhich may contain a minor amount of one or more further additives suchas one or more salts especially chloride salts such as calcium chloride,as well as a preservative for inhibiting the growth of undesirablemicroorganisms in the slurry containing the discrete alginate basedparticulates. A preferred commercially available alginate basedparticulate material comprise from about 0.5% wt. to about 5% wt. of acalcium alginate, a pigment present in an amount up to about 0.01% wt.,from about 0.1% wt. to about 5% wt. of TiO2 and the remaining balance ofthe mass of the alginate based particulate material comprised of a 2%calcium chloride solution in water which may also con an a minor amount,approx. 2% of calcium chloride. Such an alginate based particulatematerial can be separated from its aqueous-based carrier composition bymeans of a fine sieve or other means for decanting the aqueous-basedcarrier composition from the alginate based particulate materials.

By the term “suspended” when referring to inclusions is to be understoodthat when the formed inventive compositions are manually shaken and thenallowed to return to a quiescent state, such as by permitting them tostand on a tabletop or other surface at room temperature (approx. 20°C.) for 48 hours, the majority of the inclusions do not drop more than7%, preferably do not drop more than 5%, most preferably do not dropmore than 2% of their original distance from the bottom of the containerin which the inventive composition is present when they have returned toi: quiescent state following manual shaking. By “majority of inclusions”is meant to convey that at least 90% of, preferably at least 95% andmost preferably at least 97% of the inclusions physically present in thecompositions. This is a particularly attractive and characteristicfeature of preferred embodiments of inventive compositions, as thesuspended inclusions do not appear to move perceptibly over long periodsof time. Desirably, at least 90% of, preferably at least 95% and mostpreferably at least 97% of the inclusions physically present in thecompositions do not drop more than 5%, most preferably do not drop morethan 2% of their original distance from the bottom of the container inwhich the inventive composition is present when they have returned to aquiescent state following manual shaking when measured after 72 hours,more preferably when measured after 168 hours, still more preferablywhen measured after 10 days, yet more preferably after 14 days when leftin a quiescent state at room temperature. In certain particularlypreferred embodiments of the invention at least 90% of, preferably atleast 95% and most preferably at least 97% of the inclusions physicallypresent in the compositions do not drop more than 5%, after 3 weeks andespecially after 4 weeks, and especially after 6 months when retained ina quiescent state at room temperature.

Although optional, the compositions according to the present inventionmay include one or more further detersive surfactants particularly thoseselected from amongst anionic, amphoteric and zwitterionic surfactants,particularly those which may provide a detersive effect to thecompositions.

The compositions of the present invention may include at least ananionic surfactant. Generally any anionic surfactant material may beused in the inventive compositions. By way of non-limiting example,particularly suitable anionic surfactants include: alkali metal salts,ammonium salts, amine salts, or aminoalcohol salts of one or more of thefollowing compounds (linear and secondary): alcohol sulfates andsulfonates, alcohol phosphates and phosphonates, alkyl sulfates, alkylether sulfates, sulfate esters of an alkylphenoxy polyoxyethyleneethanol, alkyl monoglyceride sulfates, alkyl sulfonates, olefinsulfonates, paraffin sulfonates, beta-alkoxy alkane sulfonates,alkylamidoether sulfates, alkylaryl polyether sulfates, monoglyceridesulfates, alkyl ether sulfonates, ethoxylated alkyl sulfonates,alkylaryl sulfonates, alkyl benzene sulfonates, alkylamide sulfonates,alkyl monoglyceride sulfonates, alkyl carboxylates, alkyl sulfoacetates,alkyl ether carboxylates, alkyl alkoxy carboxylates having 1 to 5 molesof ethylene oxide, alkyl sulfosuccinates, alkyl ether sulfosuccinates,alkylamide sulfosuccinates, alkyl sulfosuccinamates, octoxynol ornonoxynol phosphates, alkyl phosphates, alkyl ether phosphates,taurates, N-acyl taurates, fatty taurides, fatty acid amidepolyoxyethylene sulfates, isethionates, acyl isethionates, andsarcosinates, acyl sarcosinates, or mixtures thereof. Generally, thealkyl or acyl radical in these various compounds comprise a carbon chaincontaining 12 to 20 carbon atoms.

Preferred anionic surfactants useful in forming the compositions of theinvention include alkyl sulfates which may be represented by thefollowing general formula:

wherein R is an straight chain or branched alkyl chain having from about8 to about 18 carbon atoms, saturated or unsaturated, and the longestlinear portion of the alkyl chain is 15 carbon atoms or less on theaverage, M is a cation which makes the compound water soluble especiallyan alkali metal such as sodium, or is ammonium or substituted ammoniumcation, and x is from 0 to about 4. Of these, most preferred are thenon-ethoxylated C12-C15 primary and secondary alkyl sulfates.

Exemplary commercially available alkyl sulfates include one or more ofthose available under the tradenames RHODAPON® (ex. Rhône-Poulenc Co.)as well as STEPANOL® (ex. Stepan Chemical Co.). Exemplary alkyl sulfateswhich is preferred for use is a sodium lauryl sulfate surfactantpresently commercially available as RHODAPON® LCP (ex. Rhône-PoulencCo.), as well as a further sodium lauryl sulfate surfactant compositionwhich is presently commercially available as STEPANOL® WA Extra (ex.Stepan Chemical Co.), which is amongst the most preferred anionicsurfactants to be used in the inventive compositions. In certainpreferred embodiments an alkyl sulfate is the sole anionic surfactantpresent.

Particularly preferred anionic surfactants useful in forming thecompositions of the invention include alkyl sulfonate anionicsurfactants which may be represented according to the following generalformula:

wherein R is an straight chain or branched alkyl chain having from about8 to about 18 carbon atoms, saturated or unsaturated, and the longestlinear portion of the alkyl chain is 15 carbon atoms or less on theaverage, M is a cation which makes the compound water soluble especiallyan alkali metal such as sodium, or is ammonium or substituted ammoniumcation, and x is from 0 to about 4. Most preferred are the C12-C15primary and secondary alkyl sulfates.

Exemplary, commercially available alkane sulfonate surfactants includeone or more of those available under the tradename HOSTAPUR® (ex.Clariant). An exemplary and particularly alkane sulfonate which ispreferred for use is a secondary sodium alkane sulfonate surfactantpresently commercially available as HOSTAPURA® SAS 60.

The anionic surfactant when present in the compositions of the presentinvention is present in an amount of from about 0.1 to about 10% byweight, more preferably is present in an amount of from about 0.1-10%wt., and most preferably is present in an amount of from about 0.5 toabout 4% wt.

For example the compositions according to the invention may optionallyfurther comprise an alkyl ethoxylated carboxylate surfactant. Inparticular, the alkyl ethoxylated carboxylate comprises compounds andmixtures of compounds which may be represented by the formula:R₁(OC₂H₄)_(n)—OCH₂COO⁻M⁺

wherein R₁ is a C₄-C₁₈ alkyl, n is from about 3 to about 20, and M ishydrogen, a solubilizing metal, preferably an alkali metal such assodium or potassium, or ammonium or lower alkanolammonium, such astriethanolammonium, monoethanolammonium, or diisopropanolammonium. Thelower alkanol of such alkanolammonium will normally be of 2 to 4 carbonatoms and is preferably ethanol. Preferably, R₁ is a C₁₂-C₁₅ alkyl, n isfrom about 7 to about 13, and M is an alkali metal counterion.

Examples of alkyl ethoxylated carboxylates contemplated to be useful inthe present invention include, but are not necessarily limited to,sodium buteth-3 carboxylate, sodium hexeth-4 carboxylate, sodiumlaureth-5 carboxylate, sodium laureth-6 carboxylate, sodium laureth-8carboxylate, sodium laureth-11 carboxylate, sodium laureth-13carboxylate, sodium trideceth-3 carboxylate, sodium trideceth-6carboxylate, sodium trideceth-7 carboxylate, sodium trideceth-19carboxylate, sodium capryleth-4 carboxylate, sodium capryleth-6carboxylate, sodium capryleth-9 carboxylate, sodium capryleth-13carboxylate, sodium ceteth-13 carboxylate, sodium C₁₂₋₁₅ pareth-6carboxylate, sodium C₁₂₋₁₅ pareth-7 carboxylate, sodium C₁₄₋₁₅ pareth-8carboxylate, isosteareth-6 carboxylate as well as the acid form. Sodiumlaureth-8 carboxylate, sodium laureth-13 carboxylate, pareth-25-7carboxylic acid are preferred. A particularly preferred sodiumlaureth-13 carboxylate can be obtained from Finetex Inc. under the tradename Surfine® WLL or from Clariant Corp. under the trade name Sandopan®LS-24.

When present, the amount of alkyl ethoxylated carboxylate present ininventive compositions are from about 0.01% wt.-10% wt., preferably fromabout 0.1-10% wt. but most preferably from about 0.5-4% wt.

By way of non-limiting example exemplary amphoteric surfactants includeone or more water-soluble betaine surfactants which may be representedby the general formula:

wherein: R₁ is an alkyl group containing from 8 to 18 carbon atoms, orthe amido radical which may be represented by the following generalformula:

wherein R is an alkyl group having from 8 to 18 carbon atoms,

-   a is an integer having a value of from 1 to 4 inclusive, and-   R₂ is a C₁-C₄ alkylene group. Examples of such water-soluble betaine    surfactants include dodecyl dimethyl betaine, as well as    cocoamidopropylbetaine.

When present, any amphoteric surfactants present in the compositions ofthe present invention are desirably included in an amount of from about0.1 to about 10% by weight, more preferably is present in an amount offrom about 0.3-5% wt., and most preferably is present in an amount offrom about 0.3% wt. to about 3% wt.

Most desirably, the total amount of detersive surfactants present in theinventive compositions, inclusive of the necessary anionic surfactantsand any further optional surfactants does not exceed about 10% wt., morepreferably does not exceed about 5% wt. of the total weight of theinventive composition.

Optionally, but in many cases desirably, the inventive compositionscomprise one or more organic solvents. By way of non-limiting exampleexemplary useful organic solvents which may be included in the inventivecompositions include those which are at least partially water-misciblesuch as alcohols (e.g., low molecular weight alcohols, such as, forexample, ethanol, propanol, isopropanol, and the like), glycols (suchas, for example, ethylene glycol, propylene glycol, hexylene glycol, andthe like), water-miscible ethers (e.g. diethylene glycol diethylether,diethylene glycol dimethylether, propylene glycol dimethylether),water-miscible glycol ether (e.g. propylene glycol monomethylether,propylene glycol mono ethylether, propylene glycol monopropylether,propylene glycol monobutylether, ethylene glycol monobutylether,dipropylene glycol monomethylether, diethyleneglycol monobutylether),lower esters of monoalkylethers of ethylene glycol or propylene glycol(e.g. propylene glycol monomethyl ether acetate), and mixtures thereof.Glycol ethers having the general structure Ra—Rb—OH, wherein Ra is analkoxy of 1 to 20 carbon atoms, or aryloxy of at least 6 carbon atoms,and Rb is an ether condensate of propylene glycol and/or ethylene glycolhaving from one to ten glycol monomer units. Of course, mixtures of twoor more organic solvents may be used in the organic solvent constituent.

When present, the organic solvent constituent is present in thecompositions of the present invention in an amount of from about 0.1 toabout 10% by weight, more preferably is present in an amount of fromabout 0.3-7% wt., and most preferably is present in an amount of fromabout 0.5% wt. to about 4% wt.

According to certain particularly preferred embodiments, the inventivecompositions exclude added organic solvents, particularly as describedimmediately above. It is recognized that organic solvents may be presentas carriers for certain other constituents essential to the presentinvention, and these may be present; generally the total amount of suchorganic solvents, if present, is less than about than 0.1% wt., morepreferably less than 0.05% wt. and most preferably comprise no organicsolvents as described above.

While optional, the compositions of the invention may further include anoxidizing agent, which is preferably a peroxyhydrate or other agentwhich releases hydrogen peroxide in aqueous solution. Such materials areper se, known to the art. Such peroxyhydrates are to be understood as toencompass hydrogen peroxide as well as any material or compound which inan aqueous composition yields hydrogen peroxide. Examples of suchmaterials and compounds include without limitation: alkali metalperoxides including sodium peroxide and potassium peroxide, alkaliperborate monohydrates, alkali metal perborate tetrahydrates, alkalimetal persulfate, alkali metal percarbonates, alkali metalperoxyhydrate, alkali metal peroxydihydrates, and alkali metalcarbonates especially where such alkali metals are sodium or potassium.Further useful are various peroxydihydrate, and organic peroxyhydratessuch as urea peroxide. Desirably the oxidizing agent is hydrogenperoxide.

Desirably the oxidizing agent, especially the preferred hydrogenperoxide is present in the inventive compositions in an amount of fromabout 0.01% wt. to about 10.0% wt., based on the total weight of thecomposition of which it forms a part.

Minor amounts of stabilizers such as one or more organic phosphonates,stannates, pyrophosphates, as well as citric acid as well as citric acidsalts may be included and are considered as part of the oxidizing agent.The inclusion of one or more such stabilizers aids in reducing thedecomposition of the hydrogen peroxide due to the presence of metal ionsand or adverse pH levels in the inventive compositions.

The compositions of the present invention can-also optionally compriseone or more further constituents which are directed to improving theaesthetic or functional features of the inventive compositions. By wayof non-limiting example such further constituents include one or morecoloring agents, fragrances and fragrance solubilizers, viscositymodifying agents, other surfactants, pH adjusting agents and pH buffersincluding organic and inorganic salts, optical brighteners, opacifyingagents, hydrotropes, antifoaming agents, enzymes, anti-spotting agents,anti-oxidants, preservatives, and anti-corrosion agents. When one ormore of the optional constituents is added, i.e., fragrance and/orcoloring agents, the aesthetic and consumer appeal of the product isoften favorably improved. The use and selection of these optionalconstituents is well known to those of ordinary skill in the art. Whenpresent, the total amount the one or more optional constituents presentin the inventive compositions do not exceed about 10% wt., preferably donot exceed 5% wt., and most preferably do not exceed about 3% wt.Certain optional constituents which are nonetheless desirably present inthe inventive compositions are pH adjusting agents and especially pHbuffers. Such pH buffers include many materials which are known to theart and which are conventionally used in hard surface cleaning and/orhard surface disinfecting compositions. By way of non-limiting examplepH adjusting agents include phosphorus containing compounds, monovalentand polyvalent salts such as of silicates, carbonates, and borates,certain acids and bases, tartrates and certain acetates. Furtherexemplary pH adjusting agents include mineral acids, basic compositions,and organic acids, which are typically required in only minor amounts.By way of further non-limiting example pH buffering compositions includethe alkali metal phosphates, polyphosphates, pyrophosphates,triphosphates, tetraphosphates, silicates, metasilicates, polysilicates,carbonates, hydroxides, and mixtures of the same. Certain salts, such asthe alkaline earth phosphates, carbonates, hydroxides, can also functionas buffers. It may also be suitable to use as buffers such materials asaluminosilicates (zeolites), borates, aluminates and certain organicmaterials such as gluconates, succinates, maleates, and their alkalimetal salts. When present, the pH adjusting agent, especially the pHbuffers are present in an amount effective in order to maintain the pHof the inventive composition within a target pH range.

As the compositions are largely aqueous in nature, and comprises as thebalance of the composition water in to order to provide to 100% byweight of the compositions of the invention. The water may be tap water,but is preferably distilled and is most preferably deionized water. Ifthe water is tap water, it is preferably substantially free of anyundesirable impurities such as organics or inorganics, especiallyminerals salts which are present in hard water which may thusundesirably interfere with the operation of the constituents present inthe aqueous compositions according to the invention. The inventivecompositions provide certain technical benefits when used on hardsurfaces, particularly: satisfactory removal of hard water stains,satisfactory removal of soap scum stains, and satisfactory disinfectionor sanitization of hard surfaces. In preferred embodiments, thecompositions are readily pumpable using a manually operable triggerspray apparatus are be desirably provided as a ready to use product in acontainer package which comprises a manually operable trigger sprayapparatus and a non-pressurized reservoir or bottle for containing theinventive compositions. In use, the consumer generally applies aneffective amount of the composition and within a few moments thereafter,wipes off the treated area with a rag, towel, brush or sponge, usually adisposable paper towel or sponge. In certain applications, however,especially where undesirable stain deposits are heavy, the compositionaccording to the invention may be left on the stained area until it haseffectively loosened the stain deposits after which it may then be wipedoff, rinsed off, or otherwise removed. For particularly heavy depositsof such undesired stains, multiple applications may also be used.

A particularly advantageous feature of the inventive compositions isthat as the suspended inclusions are visibly discrete and visiblydiscernible to the consumer, these same inclusions are visible to theconsumer on hard surfaces to which the inventive compositions have beenapplied. This permits for ready visual inspection of the coverage of thehard surface by an inventive compositions immediately after applicationof the composition by a consumer. Such provides not only an attractiveattribute to commercial products based on such compositions but alsoprovides a visual indicator to the consumer of thorough coverage andcontact with hard surfaces. This visual indicator provides an importantmeans whereby the consumer may visually inspect a surface, particularlya surface wherein the presence of undesired microorganisms is suspected,to ensure that thorough coverage and contact with said hard surface isrealized. As is known, physical contact between the inventivecomposition and undesired microorganisms is required in order to theinventive compositions to provide a disinfecting effect.

An important technical characteristic lies in rheology of the inventivecompositions. The compositions may be described as being rheopectic atlower shear rates, an especially upon standing in quiescent state, butare thixotropic at higher shear rates. Such dual properties are veryadvantageous, as when the compositions are at rest in a container, e.g.,upon standing, their rheopectic behavior provides for the stablesuspension of the inclusions described herein. When it is desired todispense the compositions from a container especially through a manuallyoperable trigger pump spray apparatus, the thixotropic characteristicsof the compositions permit for their dispensing through the nozzle ofsuch a pump spray apparatus. An exemplary manually operable trigger pumpspray apparatus, such as a “Specialty Trigger Pump Spray/Off” (ex.Owens-Illinois Corp.). Ideally, after being dispensed from such a pumpspray apparatus and onto a surface, especially an inclined surface thecompositions return to a quiescent state and once again display arheopectic behavior. Furthermore, as at least some of the suspendedinclusions are delivered from the composition and onto the surface,these inclusions are present on the surface and provide a usefulindicator as to the coverage of the sprayed composition onto thesurface.

Alternatively in certain preferred embodiments the compositions of theinvention may be provided in a conventional aerosol as well, and apropellant added to the constituents making up the composition. Howeverthe latter use of the inventive compositions in an aerosol dispenser isunlikely to be adopted for practical use as current conventional aerosoldispenser are typically metal canisters which do not readily permit forthe consumer to enjoy the appearance of the visibly discernible, visiblydiscrete particulate materials as suspended inclusions when thecompositions are in a quiescent state. Nonetheless, the use ofcompositions provided in aerosol canisters does provide the benefit ofpressurized dispensing of the composition, and the composition appliedto a hard surface does present the visibly discernible, visibly discreteparticulate materials on a treated surface. Nonetheless, the use of amanually operable trigger pump spray apparatus with the inventivecompositions is usually preferred.

The inventive compositions are desirably provided as a ready to useproduct which may be directly applied to a hard surface. By way ofexample, hard surfaces suitable for coating with the polymer includesurfaces composed of refractory materials such as: glazed and unglazedtile, brick, porcelain, glazed ceramics, vitreous ceramics such aschina; glass; metals; plastics, e.g. polyester, vinyl, fiberglass,Formica®, Corian®; and other hard surfaces known to the industry. Suchknown hard surfaces are usually non-porous. Hard surfaces which are tobe particularly denoted are lavatory fixtures such as shower stalls,bathtubs and bathing appliances (racks, curtains, shower doors, showerbars) toilets, bidets, wall and flooring surfaces especially those whichinclude refractory materials and the like. Further hard surfaces whichare to be denoted are those associated with kitchen environments andother environments associated with food preparation, including cabinetsand countertop surfaces as well as walls and floor surfaces especiallythose which include refractory materials, plastics, and glass. Stillfurther hard surfaces include those associated with medical facilities,e.g., hospitals, clinics as well as laboratories, e.g., medical testinglaboratories.

The compositions according to the invention are easily produced by anyof a number of known art techniques. Conveniently, a part of the wateris supplied to a suitable mixing vessel further provided with a stirreror agitator, and while stirring, the remaining constituents are added tothe mixing vessel, including any final amount of water needed to provideto 100% wt. of the inventive composition. The order of addition is oftennot critical but preferably, under constant stirring, to a portion ofthe water is first added the thickener constituent, thereafter stirringis allowed to continue until the thickener constituent is homogenouslydistributed in the water. Preferably a homogenizer or other high shearmixing device is used however so to ensure the uniform mixing of thethickener constituent in the compositions taught herein. Subsequentlythe nonionic surfactant is added, then the organic solvent if present,then the anionic surfactant followed by the remaining constituents,including optional constituent. Thereafter, the suspended inclusions areintroduced, desirably as an aqueous slurry containing the alginate basedinclusions in an aqueous carrier, and finally the remaining quantity ofwater needed to provide 100% wt. of the composition. While the processmay be practiced at room temperature (approx. 20° C.) it may beadvantageous to heat the initial charge of water to an elevatedtemperature, e.g., even in excess of 90° C. to facilitate theincorporation of one or more of the constituents, particularly thethickener constituents into the water.

The following examples below illustrate exemplary formulations andpreferred formulations of the inventive composition. It is to beunderstood that these examples are presented by means of illustrationonly and that further useful formulations fall within the scope of thisinvention and the claims may be readily produced by one skilled in theart and not deviate from the scope and spirit of the invention.Throughout this specification and in the accompanying claims, weightpercents of any constituent are to be understood as the weight percentof the active portion of the referenced constituent, unless otherwiseindicated.

EXAMPLES

Exemplary formulations illustrating certain preferred embodiments of theinventive compositions and described in more detail in Table I belowwere formulated generally in accordance with the following protocol.

Into a suitably sized vessel, a measured amount of water was provided ata temperature of between about 5° C.-30° C. and under stirring using alaboratory scale homogenizer device, the thickener constituents werefirst added, and homogenization was permitted to continue for about30-90 minutes until the thickened mixture became homogenous. Thethickened mixture was then removed from the homogenizer device andintroduced into a laboratory beaker provided a motor driven propeller asa stirrer. Thereafter under constant uniform stirrig the remainingconstituents were added in the following sequence: surfactants, organicsolvent (when present), acid, caustic (sodium hydroxide) and then theremaining constituents, with the suspended inclusions, e.g., alginatebeads in a slurry being added as the last constituent. Thereafter theremaining amount of water needed to provide 100% wt. of the composition.Mixing of the constituents in the laboratory beaker took from about30-90 minutes, and the total time of mixing generally lasted from about60 minutes to about 180 minutes. In each case, mixing was maintaineduntil the particular composition appeared to be homogeneous, and thesuspended inclusions well dispersed. The exemplary compositions werepourable, readily pumpable using a manually operable trigger sprayapparatus and retained exceptionally well mixed characteristics (i.e.,stable mixtures) upon standing. Notwithstanding the above preferredprotocol, other sequences of mixing and orders of addition of theconstituents may be practiced.

Examples of inventive formulations are shown in Table 1 below (unlessotherwise stated, the components indicated are provided as “100%active”) wherein the amounts of the named constituents are indicated in%wlw. Deionized water was added in “quantum sufficient” to provide thebalance to 100 parts by weight of the compositions. TABLE 1 Ex. 1 Ex. 2Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 gellan gum 0.05 0.05 0.05 0.05 0.050.05 0.05 0.05 xanthan gum 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10linear primary C₈-C₁₀ alcohol 1.0 1.0 — — 1.0 1.0 1.0 1.0 ethoxylated,avg. 4.5 moles ethoxylation^((a)) fatty alcohol ethoxylate^((b)) — — 1.0— — — — — linear alcohol alkoxylate^((c)) — — — 1.0 — — — — sodiumlauryl sulfate^((d)) 2.75 — — — — — — —decyl(sulfophenoxy)benzenesulfonic acid, — 2.75 — — — — — — disodiumsalt^((e)) 2-hydroxy-1,2,3-propanetricarbolic acid 3.5 3.5 3.5 3.5 3.53.5 — — hydroxyacetic acid — — — — — — 3.5 — hydroxypropionic acid — — —— — — — 3.5 caustic soda 0.42 0.44 0.46 0.53 0.39 0.45 0.43 0.34fragrance 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 alginate beads 0.410.41 0.41 0.41 0.41 0.41 0.41 0.41 di water q.s. q.s. q.s. q.s. q.s.q.s. q.s. q.s. pH 3.15 3.14 3.12 3.28 3.20 3.09 3.09 3.10

The identity of the individual constituents indicated above is listed onthe following table: TABLE 2 gellan gum Kelcogel AFT (100%) (ex. Kelco)xanthan gum Kelzan ASXT (100%) (ex. Kelco) linear primary C₈-C₁₀ alcoholAlfonic 810-4.5 (100%) (ex. Sassol) ethoxylated, avg. 4.5 molesethoxylation^((a)) fatty alcohol ethoxylate^((b)) Genapol 26-L-80 (100%)(ex. Clariant) linear alcohol alkoxylate^((c)) Plurafac SL-62 (100%)(ex. BASF) sodium lauryl sulfate^((d)) Stepanol WAC (30%) (ex. StepanCo.) decyl (sulfophenoxy) Hostapur SAS 60 (60%) (ex. Clariant)benzenesulfonic acid, disodium salt^((e)) 2-hyroxy-1,2,3- citric acid(100%) (ex. ADM) propanetricarbolic acid hydroxyacetic acid glycolicacid (70%) (ex. DuPont) hydroxypropionic acid lactic acid (88%) causticsoda sodium hydroxide (25%) “rayon grade” fragrance proprietarycomposition alginate beads an aqueous suspension of alginate beads in anaqueous carrier containing a 2% concentration of calcium chloride; thedrained weight of the beads comprises 73% of the total weight of theaqueous suspension of alginate beads (ex. geniaLabs Biotechnologie,Germany) di water deionized water

Certain of the compositions described on Table 1 above were tested toevaluate certain technical characteristics of the compositions.

Evaluation of Viscosity:

The viscosity of certain of the compositions were evaluated utilizingusing an LVTDV II Brookfield Viscometer, #1 spindle at 30 rpm and 25° C.The viscosity of certain of the exemplary compositions is reported inthe following table: TABLE 3 Example formulation: Viscosity Ex. 1 143cps Ex. 2 86.8 cps Ex. 3 91.2 cps Ex. 4 84.8 cps Ex. 5 98.2 cps Ex. 688.2 cps Ex. 7 95.9 cps Ex. 8 88.2 cpsEvaluation of Sprayability:

A quantity of a sample composition was placed into the interior of anon-pressurized bottle to which was affixed a manually operable“Specialty Trigger Pump Spray/Off” (ex. Owens-Illinois Corp.) triggerspray device. A vertical glass panel was used with the device toevaluate the sprayability characteristics of a sample composition. Atvarying distances from as little as 4 inches to as far as 24 inches, acomposition was dispensed from the trigger spray device which was heldperpendicularly to the vertical glass panel. The delivery of thecomposition from the trigger spray device, and the wettingcharacteristics of the composition were observed and evaluated. To beconsidered a “pass” the composition need be dispensed in a generallyuniform spray from the trigger spray device within the range of 4-24inches, and especially at about 18 from the vertical glass panel, and togenerally even wet out the surface and not form a preponderance of beadsor droplets which clung to the vertical glass panel without dispersingafter contact.

Each of the formulations according to the invention described on Table 1were considered to “pass” the spray test described above.

Evaluation of Efficacy Against Soap Scum:

The efficacy of inventive compositions in removing-soap scum from a hardsurface was evaluated in accordance with CSMA Methods DCC-16 (May 1995)titled “Guidelines for Evaluating the Efficacy of Bathroom Cleaners—Part2: Scrubber Test for Measuring the Removal of Lime Soap”. This test isdescribed generally as follows:

First, a “parent” soil is made, based on the following formulation:“Parent” soil % w/w bar soap 3.90 shampoo 0.35 clay 0.06 artificialsebum 0.15 hard water 95.54

The parent soil was produced according to the following steps: First,the bar soap was shaved into a suitable beaker. Afterward the remainingconstituents were added in the order given above and stirred withthree-blade propeller mixer. Next, the contents of the beaker was heatedto 45-50° C. and mixed until a smooth, lump-free suspension wasachieved. This usually required about two hours with moderate agitation.Subsequently, the contents of the beaker were filtered through a Buchnerfunnel fitted with Whatman #1 filter paper or equivalent. The filtratewas then resuspended in clean, deionized water, using the same amount ofwater used to make the soil, and this was filtered again. The(re-filtered) filtrate was uniformly dried overnight at 45° C. to form afilter cake. Thereafter, the filter cake was pulverized and was suitablefor immediate use, or may be stored in a sealed container for up to sixmonths.

The test substrates (tiles) were prepared in the following manner: eachtile was thoroughly washed (using a commercially available handdishwashing detergent such as, Dove®) and scrubbed using a non-metallicscouring pad (such as a Chore Boy® Long Last scrubbing sponge). Thewashed tiles were then permitted to dry in an oven at 40.5° C.overnight, then withdrawn and allowed to cool to room temperature<approx. 20° C.) before being provided with the standardized “hardwater” test soil. It is to be noted that for each test, new tiles wereutilized, namely, the tiles were not reused. In preparation forsupplying the tiles with an amount of the test soil, a test soil wasprepared based on the following formulation: Test soil: % w/w “parent”soil 4.50 hard water 9.0 hydrochloric acid (0.1N) 0.77 acetone 85.73The test soil was produced according to the following steps: Theconstituents indicated were introduced into a clean beaker, with theacetone being added prior to the water, and the ‘parent’ soil beingadded last. The contents of the beaker were mixed using a standard threeblade laboratory mixer until the contents formed a uniform mixture, andthe color changed from white to gray. This typically required 20-40minutes, during which time the beaker was covered as much as possible toavoid excessive solvent loss. Next, a suitable quantity of the contentsof the test soil from the beaker was provided to an artist's airbrushwhile the beaker was swirled to ensure soil uniformity. (If testingrequired more than one day, a fresh amount of test soil was prepareddaily and used for that day's testing.)

Soil was applied to a number of clean, dry tiles placed into rows andcolumns in preparation for depositing of the test soil. The airbrush wasoperated at 40 psi, and the test soil was sprayed to provide a visuallyuniform amount of soil onto the tiles. (Uniform soil suspension duringapplication was maintained by continuous brush motion and/or swirling oftest soil in the airbrush.) In this manner, approximately 0.10 g-0.15 gtest soil were applied per tile.

The tiles were then allowed to air dry for approximately 30 minutes,during which time the a laboratory hotplate was preheated toapproximately 320° C. Each tile was sequentially placed on the hotplateuntil the test soil began to melt, thereby “aging” the test soil. Themelting of the test soil was observed carefully, and each tile wasremoved shortly before the soil began to coalesce into large droplets.This process was repeated for each tile, allowing the hotplate torecover to 320° C. between tiles. Subsequently each tile was permittedto cool for at least about 30 minutes.

To evaluate cleaning, a treated test tile was placed in a GardnerApparatus and secured. A dry 10 cm by 7.6 cm sponge was first moistenedwith 100 g of tap water, and the excess wrung out from the sponge. Thesponge was then fitted into a suitably sized holder in the GardnerApparatus. A 4-5 gram aliquot of a test formulation was then depositeddirectly onto the soiled surface of a tile, and allowed to contact thetile for 15 seconds. Thereafter, the Gardner Apparatus was cycled forfrom 3-6 strokes. The tile was then rinsed with tap water, and driedwith compressed air from an airbrush compressor. This test was repeatedseveral times for each formulation, using new treated test tile for eachevaluation.

The tested tiles were evaluated by either reflective means, i.e., usinga Minolta Chromameter in order to determine the change in reflectancebetween an unsoiled, untreated tile which was used as a “control”, andthe reflectance of a soiled tile which was cleaned using a quantity ofan inventive composition in accordance with the test protocol describedabove. According to the reflective means, the percentage of hard watersoil removal was determined utilizing the following equation:${\%\quad{Removal}} = {\frac{{RC} - {RS}}{{RO} - {RS}} \times 100}$where

-   -   RC=Reflectance of tile after cleaning with test product    -   RO=Reflectance of original soiled tile    -   RS=Reflectance of soiled tile

For each tile, a number of readings were taken and the results averagedto provide a median reading for each tile. Five tiles were used toevaluate each of the tested compositions and the average reading foreach tile, as well as the averaged reflectance reading for all fivetiles treated using a particular composition described in Table 1 arereproduced below. These results may be compared to the reflectance of anunsoiled, untreated tile which exhibited an averaged reflectance of93.3% which was used as a “control”. The tested tiles were evaluated,and the results are indicated on the Table 4, below. TABLE 4 AveragedTile: reflectance 1 2 3 4 5 reading Ex. 1 63.9% 72.4% 69.3% 76.2% 71.8%70.72% Ex. 5 59.6% 50.0% 64.2% 63.1% 60.8% 59.54% Control: 93.3% — — — — 93.3%Evaluation of Antimicrobial Efficacy:

Several of the exemplary formulations described in more detail on Table1 above were evaluated in order to evaluate their antimicrobial efficacyagainst Staphylococcus aureus (gram positive type pathogenic bacteria)(ATCC 6538), Salmonella choleraesuis (gram negative type pathogenicbacteria) (ATCC 10708), Pseudomonas aeruginosa (ATCC 15442). The testingwas performed in accordance with the protocols outlined in AOAC OfficialMethod 961.02 “Germicidal Spray Products as Disinfectants”, as describedin AOAC Official Methods of Analysis, 16th Ed., (1995).

As is appreciated by the skilled practitioner in the art, the results ofthe AOAC Germicidal Spray Test indicates the number of test substrateswherein the tested organism remains viable after contact for 10 minuteswith a test disinfecting composition/total number of tested substrates(slides) evaluated in accordance with the AOAC Germicidal Spray Test.Thus, a result of “0/15” indicates that of 15 test substrates bearingthe test organism and contacted for 10 minutes in a test disinfectingcomposition, 0 test substrates had viable (live) test organisms at theconclusion of the test. Such a result is excellent, illustrating theexcellent disinfecting efficacy of the tested composition.

Results of the testing are indicated on Table 5, below. The reportedresults indicate the number of test cylinders with live testorganisms/number of test cylinders tested for each example formulationand organism tested. TABLE 5 Test Results Conclusion Staphylococcusaureus 0/15 pass Salmonella choleraesuis 0/15 pass Pseudomonasaeruginosa 0/15 pass

As may be seen from the results indicated above, the compositionsaccording to the invention provide excellent cleaning benefits to hardsurfaces, including hard surfaces with difficult to remove stains. Theseadvantages are further supplemented by the excellent antimicrobialefficacy of these compositions against known bacteria commonly found inbathroom, kitchen and other environments. Such advantages clearlyillustrate the superior characteristics of the compositions, thecleaning and antimicrobial benefits attending its use which is notbefore known to the art.

1. A sprayable hard surface cleaning and/or disinfecting compositionwhich comprises: a thickener constituent which comprises both gellan gumand xanthan gum; at least one nonionic surfactant; an acid constituent;suspended inclusions which appear as visibly discernible, discreteparticulate materials, preferably where said discrete particulatematerials are based on alginates; optionally, at least one anionicsurfactant; optionally, at least one further detersive surfactantselected from amphoteric and zwitterionic surfactants; optionally, butdesirably at least one organic solvent; optionally, one or moreconstituents for improving the aesthetic or functional features of theinventive compositions; and; water.
 2. The composition according toclaim 1 wherein the acid constituent contains an acid selected from thegroup consisting of: citric acid, sorbic acid, acetic acid, boric acid,formic acid, maleic acid, adipic acid, lactic acid, malic acid, malonicacid, glycolic acid, and mixtures thereof.
 3. The composition accordingto claim 2 wherein the acid constituent comprises citric acid.
 4. Thecomposition according to claim 1 wherein the composition comprises anorganic solvent.
 5. The composition according to claim 4 wherein theorganic solvent is selected from alcohols, glycols, water miscibleethers, water miscible glycol ethers, monoalkylether esters, andmixtures thereof.
 6. The composition according to claim 5 wherein theorganic solvent is selected from alcohols, water miscible glycol ethersand mixtures thereof.
 7. The composition according to claim 1 whereinthe pH is less than about than
 6. 8. The composition according to claim7 wherein the pH is from about 2 to about 3.5,
 9. The compositionaccording to claim 8 wherein the pH is from about 2.8 to about 3.3. 10.The composition according to claim 1 wherein the anionic surfactant isan alkane sulfonate.
 11. The composition according to claim 1 whereinthe anionic surfactant is a secondary sodium alkane sulfonate.
 12. Thecomposition according to claim 1 wherein the nonionic surfactant is anonionic block copolymers based on a polymeric ethoxy/propoxy units. 13.The composition according to claim 1 which is essentially free oforganic solvents.
 14. A hard surface cleaning and/or disinfectingcomposition according to claim 1 wherein said composition exhibitsantimicrobial efficacy against at least one of the following organisms:Staphylococcus aureus (gram positive type pathogenic bacteria),Salmonella choleraesuis (gram negative type pathogenic bacteria),Pseudomonas aeruginosa in accordance with the protocols outlined in AOACOfficial Method 961.02.
 15. (canceled)
 16. A method of treating a hardsurface comprising applying an effective amount of a compositionaccording to claim 1 to the surface in need of treatment.
 17. Thecomposition according to claim 1 wherein the respective weight ratio ofgellan gum to xanthan gum is from 1:1-10 parts by weight.
 18. Thecomposition according to claim 17 wherein the respective weight ratio ofgellan gum to xanthan gum is from 1 1:1-5 parts by weight.
 19. Thecomposition according to claim 18 wherein the respective weight ratio ofgellan gum to xanthan gum is from 1:1 to 1:2 parts by weight.